Synthesis of Tetragonal Phase Stabilized Nano and Submicron Sized Nanoparticles

ABSTRACT

Novel, monodispersed, spherical ZrO 2  particles in the size range of approximately 10 to approximately 600 nm exhibiting metastable tetragonal crystal structure at room temperature and novel methods of preparation. The ZrO 2  particles are approximately 100% in the tetragonal phase at room temperature and can be pure and free of foreign oxides. The novel method can include mixing zirconium-alkoxide and an alcohol, forming preparation one, followed by separately dissolving completely de-ionized water and a polymeric steric stabilizer in an alcohol forming preparation two. Next the preparations can be mixed with vigorous stirring while subjecting the materials to hydrolysis and condensation reactions with very slow stirring. Next, there is waiting for the formation of a sol from the mixture, followed by drying at approximately 80 degrees C. to form resultant material followed by crushing the resultant material.

This invention claims the benefit of priority from U.S. Provisionalapplication 60/408,325 filed Sep. 5, 2002, and was supported in part byNational Science Foundation (NSF) Grant # EEC:0136710.

FIELD OF INVENTION

This invention relates to nanoparticles and more particular tomonodispersed, spherical ZrO₂ particles in the size range ofapproximately 10 to approximately 600 nm. exhibiting metastabletetragonal crystal structure at room temperature and this inventionprovides the synthesis, for the first time, using the sol-gel techniqueand without doping any trivalent impurities, of monodispersed, sphericalZrO₂ particles in the size range of approximately 10 to approximately600 nm, exhibiting metastable tetragonal crystal structure at roomtemperature. This invention has revealed using high-resolutiontransmission electron microscopy that “hard-aggregates” forming tendencyof ZrO₂ nanocrystallites of size approximately 30 to approximately 45 nmis responsible for stabilizing the high-temperature metastabletetragonal phase, at room temperature within large sized (500-600)undoped ZrO₂ particles.

BACKGROUND AND PRIOR ART

Zirconium (ZrO₂) is a well-known structural ceramic, which exhibitstetragonal-to-monoclinic martensitic phase transformation. This phasetransformation is of technological importance as it contributes to thetoughening of ceramics. Porter, D. L., Evans, A. G., Heuer, A. H., ActaMetall, 1979, 27, 1649. The tetragonal-to-monoclinic phasetransformation is accompanied by volume expansion and can be triggeredby hydrostatic and shear stresses. See Simha, N., Truskinovsky, L. ActaMetall. Mater. 1994, 42, 3827.

This type of transformation can take place near the crack tip due tolocal stress concentration, which can blunt the crack tip as a result ofthe development of compressive stresses associated with the phasetransformation; thus, delaying the crack propagation and resistingsubsequent fracture.

Zirconia is used as a dispersed phase in oxide (alumina) (Kosmac, T,Swain, M. V. Clausssen, N, Mater. Sci Eng. 1984, 71, 57). as well asnon-oxide (carbides, borides, and nitrides) (Swain, M. V. Mater. Forum1988, 11, 182.) ceramics to increase their fracture toughness, strength,and hardness. This stress induced transformation has also been shown toincrease the plasticity from the shape deformation and accommodationstrains, which are associated with the transformation. (Muddle, B. C.Kelly, P. M. MaterForum 1988, 11, 182.) Increase in the wear andcorrosion resistance of nanostructured ceramic coatings as a result ofstress-induced phase transformation has also been reported. (Aita, C.R., In Advances in Catings: TMS Annual Meeting, Warrendale, Pa., 1995 p.235) Besides this, tetragonal ZrO₂ also finds application ascatalyst/catalyst support for various gas-phase reactions. (Haruta, M.Kobayashi, T, Sano, H., Yamada, N Chem Lett. 1987, 829, 405 and Knell,A, Barnickel, P, Baiker, A, Wokaum, A. J. Catal. 1992, 137, 306.) Hence,synthesizing ZrO2 particles with metastable tetragonal crystal structureis important.

Doping zirconia with trivalent impurities has been a traditionalapproach for the metastable tetragonal phase stabilization. (Ping, L,Chen, L. W., Penner-Hahn, J. E., J. Am Ceram Soc. 1994, 77, 188.)Particle size has also been observed to have its own effect on themetastable tetragonal phase stability in nanocrystalline zirconia.(Garvie, R. C., J. Phys. Chem 1965, 69, 1238, and Nitsche, R, Rodewald,M, Skandan, G, Guess, H., Hahn, H. Nanostruct. Mater. 1996, 7, 535, andNitsche, R, Winterer, M, Hahn, H, Nanostruct. Mater. 1995, 6, 1979). Dueto the existence of a critical nanoparticle size for the metastabletetragonal phase stabilization, the tetragonal phase stabilizationwithin the submicron sized ZrO₂ particles has been unachievable.

SUMMARY OF THE INVENTION

The first objective of this invention is to provide ultra fineapproximately 10 to approximately 600 nm and more particularlyapproximately 10 to approximately 30 nm and sub-micron sized(approximately 500 to approximately 600 nm) ZrO₂ nanoparticles that arein the metastable tetragonal phase.

The second objective of this invention is to provide a method forsynthesizing particles of the size range of approximately 10 toapproximately 600 nm and more particularly nano (approximately 10 toapproximately 30 nm) and sub micron (approximately 500 to approximately600 nm) ZrO₂ nanoparticles in the metastable tetragonal phase.

The third objective is to provide coatings of ZrO₂ coatings on metalsubstrates.

A preferred embodiment of the invention includes monodispersed,spherical zirconia (ZrO₂) particles of approximately 10 to approximately600 nm, which exhibit metastable tetragonal crystal structure at roomtemperature. The ZrO₂ particles are approximately 100% in the tetragonalphase at room temperature, and the particles are pure and free offoreign oxides.

A preferred method for the synthesis of monodispersed, spherical ZrO₂particles, which exhibit approximately 100% metastable tetragonalstructure at room temperature, of sizes of approximately 10 toapproximately 600 nm, in powder form can include various steps. Theinitial step can include mixing zirconium-alkoxide and an alcohol,forming preparation one, followed by separately dissolving completelyde-ionized water and a polymeric steric stabilizer in an alcohol formingpreparation two. Next the preparation one and the preparation two can bemixed with vigorous stirring for a approximately few minutes only,subjecting the materials to hydrolysis and condensation reactions withvery slow stirring. Next, there is waiting for the formation of a solfrom the mixture. Next, there is drying at approximately 80 degrees C.to form resultant material followed by crushing the resultant material.

The polymeric steric stabilizer can be an organic polymer containing —OHor ether group. The polymeric steric stabilizer can be from one of thegroup consisting of hydroxypropyl cellulose polymer (HPC),polyvinylalcohol, ethylene glycol, and hexamethyldisilazane. Thezirconium-alkoxide can be zirconium (IV) n propoxide and the alcohol canbe anhydrous alcohol. Synthesis can take place under normal atmosphericconditions. The polymeric steric stabilizer can be an HPC polymer, andhave a molecular weight of approximately 80,000 to approximately1,000,000.

Further objects and advantages of this invention will be apparent fromthe following detailed description of the presently preferredembodiments which are illustrated schematically in the accompanyingdrawings.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 a shows nanocrystalline (approximately 20 to approximately 25 nm)sized spherical ZrO₂ particles synthesized using the sol-gel techniqueunder the processing conditions of R=60 and HPC=1.0 g/L.

FIG. 1 b shows monodispersed, submicron sized approximately 500 toapproximately 600 nm spherical ZrO₂ particles synthesized using thesol-gel technique under processing conditions of R=5, and HPC=1.0 g/L.

FIG. 2 a shows HRTEM analysis of monodispersed submicron sized sphericalZrO₂ particles synthesized under the processing conditions of R=5 andHPC=1.0 g/L after calcinations at 400 degrees for 2 hours.

FIG. 2 b shows the SAED patterns obtained for monodispersed, submicronsized (approximately 500-approximately 600 nm) spherical ZrO₂ particlesat the edge of a particle after calcination at 400 degrees C. for 2hours.

FIG. 2 c shows SAED patterns obtained for monodispersed submicron sized(approximately 500 to approximately 600 nm) spherical ZrO₂ particles atthe center of a particle after calcinations at 400 degrees C. for 2hours.

FIG. 3 shows typical broad scan XRD patterns, within 20 range of 10degrees to 80 degrees, obtained for nanocrystalline ZrO₂ particles ofsize approximately 20 to approximately 25 nm after calcinations at 400degrees C. for 2 hours, synthesized under the processing conditions ofR=60, and HPC=1.0 g/L.

FIG. 4 shows typical broad scan XRD patterns, within 2ι range ofapproximately 10° to approximately 80°, obtained for monodispersed,submicron sized (approximately 500 to approximately 600 nm), sphericalZrO₂ particles, after calcination at 400° C. for 2 h, synthesized underthe processing conditions of R=5, and HPC=1.0 g/L.

FIG. 5 shows typical narrow scan XRD patterns obtained formonodispersed, submicron sized (approximately 500 to approximately 600nm), spherical ZrO₂ particles, after calcination at higher temperaturesfor 2 h, synthesized under the processing conditions of R=5, and HPC=1.0μL.

FIG. 6 a provides schematic diagrams showing the ZrO₂ nanocrystallitesforming loose-aggregates.

FIG. 6 b provides schematic diagram showing the ZrO₂ nanocrystallitesforming hard-aggregates.

FIG. 6 c provides a schematic representation of the athermal nature oftetragonal to monoclinic phase transformation in nanocrystalline ZrO₂.The calcination temperature increases from (i) to (iii) represents thetemperature range of 400-800° C.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Before explaining the disclosed embodiments of the present invention indetail it is to be understood that the invention is not limited in itsapplication to the details of the particular arrangements shown sincethe invention is capable of other embodiments. Also, the terminologyused herein is for the purpose of description and not of limitation.

This invention demonstrates for the first time that, at roomtemperature, the stability of the metastable tetragonal phase within thesubmicron sized ZrO₂ particles strongly depends on the aggregationtendency of ZrO₂ nanocrystallites. As a result of strong aggregation ofZrO₂ nanocrystallites, the inventors have been able to synthesize bothnano (approximately 10 to approximately 30 nm) and large sized(approximately 500 to approximately 600 nm) ZrO₂ particles having 100%tetragonal crystal structure. This particle size is much larger than thecritical size of approximately 6 nm, reported in the prior art, for thestabilization of 100% tetragonal phase.

To prepare the nanoparticles of the invention, pure zirconium(IV)n-propoxide anhydrous ethanol (approximately 200 proof) and the HPCpolymer (hydroxyproylcellulose, molecular weight approximately 80,000g/mol) used as a polymeric steric stabilizer were obtained from AldrichCo and were used as received

Other alcohols and zirconium alkoxides may also be used. Other polymericsteric stablilzers may also be used such as any compound with —OH orether groups, for example polyvinylalcohol, ethylene glycol, orhexamethyldisilazane.

Other ceramic oxides can be used in addition to zirconium, for example,tin, indium, and titanium.

Nanocrystalline ZrO₂ powder is synthesized by hydrolysis of zirconium(IV) n-propoxide in an alcohol solution. The beakers used in theexperiments were cleaned, washed with deionizer water, dried completelyand rinsed with anhydrous 200 proof ethanol. During synthesis, twodifferent but equal parts of alcohol solutions were prepared. In thefirst part, deionized water was dissolved into anhydrous 200 proofethanol using two different R values (R)=5 and 60, which is the ratio ofmolar concentration of water to zirconium(IV) n-propoxide. HPC polymer(HPC)=1.0 g/L was then added to this part and was dissolved completelyby stirring the solution overnight using a magnetic stirrer. The secondpart of the alcohol solution was then prepared by completely dissolvingzirconium (IV) n-propoxide (0.1 M) in anhydrous 200 proof ethanol undernormal atmospheric conditions and homogenized using magnetic stirringfor a few minutes only. After preparing each solution, both the beakerswere sealed immediately with paraffin tape. Hydrolysis of zirconium(IV)n-propoxide was then carried out under atmospheric conditions by rapidlymixing the two sealed solutions under vigorous stirring. The formationof ZrO2 particles was evident from the white color of the resulting soldue to immediate precipitation.

The sol was stirred very slowly for approximately 4 hours and then heldunder static conditions for 24 h to ensure completion of the hydrolysisand condensation reactions. The sol was subsequently dried atapproximately 80° C. using Petri dishes in order to remove the solventcompletely. The small gel pieces obtained were then crushed to obtainthe nanocrystalline ZrO₂ powder, which was calcined at differenttemperatures ranging from approximately 400° to approximately 800° C. inair for the phase evolution study. The samples were heated at a rate ofapproximately 30° C./min up to the calcination temperature, held at thattemperature for 2 hours, and then slowly cooled to room temperature inthe furnace. The as-synthesized nanocrystalline ZrO2 powders were thenexamined using a Phillips EM400 transmission electron microscope (TEM)at 120 kV. A high-resolution field TEM (HRTEM) (FEI-Philips Tecnai F30)was used to observe lattice images showing different orientations ofnanocrystals within a submicron sized ZrO₂ particle, after calcinationat approximately 400° C. for 2 h. Bright field TEM images at 300 kV weretaken to observe the lattice. Selected-area electron diffraction (SAED)patterns were taken to analyze the crystal structure. SAED patternscollected near the edge and from the center of the particle, providedthe presence of nanocrystals within a submicron sized particle.

The crystalline phases present in the as-synthesized and calcinedpowders were also determined using a standard Rigaku X-raydiffractometer (XRD). Line traces were obtained over 2 ι values rangingfrom approximately 10° to approximately 80°. Narrow scan analysis wasconducted in the 2ι range of approximately 29.5° to approximately 31.5°,as it contained the strongest line for the tetragonal (111)t phase. Thisintense peak was then curve fitted using the peak-fit software(peak-fit, version-4, SPSS Inc.). The average tetragonal crystallitesize (Dt) was calculated from the (111)t diffraction peak usingScherrer's equation, where, D is the average crystallite size in nm, Ïis the radiation wavelength (approximately 0.154 nm), β′ is thecorrected halfwidth at half-intensity (fwhm) and ι is the diffractionpeak angle.

TEM images of nanocrystalline and submicron sized ZrO₂ particlessynthesized via the sol-gel technique, under the processing conditionsof R) 60 and R) 5, at [HPC])g/L, are shown in FIGS. 1 a and 1 b,respectively. ZrO₂ nanocrystallites of size approximately 20 toapproximately 25 nm are synthesized under the processing conditions ofR) 60, [HPC]) approximately 1.0 μL, FIG. 1 a. ZrO₂ nanocrystallites form“loose-agglomerates” under these processing conditions. On the otherhand, monodispersed, submicron sized (approximately 500 to approximately600 nm), spherical ZrO₂ particles are formed under the synthesisconditions of R) 5, [HPC]) 1.0 g/L, FIG. 1 b. An HRTEM image obtainedfrom the edge of one of the ZrO₂ particle, FIG. 1 b, after annealing at400° C. for 2 h, is shown in FIG. 2 a.

Two tetragonal lattices are observed in FIG. 2 a having differentrelative orientations. SAED images obtained form the edge and the centerof ZrO2 particle, FIG. 1 b, after annealing at approximately 400° C. for2 h, are shown in FIGS. 2 b and 2 c, respectively. More diffractionspots are observed in the SAED pattern obtained from the center of theZrO₂ particle, FIG. 2 c, than are obtained from the edge of theparticle, FIG. 2 b. In fact, we observed a gradual increase in thenumber of diffraction spots when traversed from the edge toward thecenter of the particle. This indicates that a larger number ofnanocrystallites are located at the center of the particle than that atthe particle edge. Typical broad-scan XRD patterns obtained for ZrO2particles synthesized under the two different processing conditions,FIG. 1 a, 1 b are presented in FIGS. 3 and 4 respectively, as a functionof calcination temperature. The as-synthesized ZrO2 particles areobserved to be X-ray amorphous; however, they crystallize at thecalcinations temperature of approximately 400 degrees C. ZrO₂nanocrystallites of size approximately 20 to approximately 25 nm exhibittetragonal and monoclinic crystal structure after calcinations atapproximately 400 degrees C. for 2 h, as shown in FIG. 3.Tetragonal-to-monoclinic phase transformation is observed atapproximately 600 degrees C., which increases the relative volumefraction of monoclinic phase at the expense of the tetragonal phase. Thephase transformation almost goes to completion after calcinations atapproximately 800 degrees C.

Thus, gradual transformation of tetragonal phase to monoclinic phase isobserved for ZrO₂ nanocrystallites of size approximately 20 toapproximately 25 nm with increasing calcinations temperature within therange of approximately 400 to approximately 800 degrees C. On the otherhand, monodispersed, submicron sized (approximately 500 to approximately600 nm) spherical ZrO₂ particles do not exhibit gradual phasetransformation as a function of increasing calcination temperature, FIG.4. The high-temperature metastable tetragonal phase is observed tonucleate from the amorphous phase at approximately 400° C. and is alsoobserved to be stable after calcination at approximately 600° C. Nomonoclinic phase is detected at the calcination temperatures ofapproximately 400° C. and approximately 600° C. However, when calcinedat approximately 800° C., almost complete tetragonal to monoclinic phasetransformation is observed.

Typical narrow XRD scans of the (111)t peak, corresponding to thetetragonal phase, for monodispersed, submicron sized, spherical ZrO₂particles, after calcination at approximately 400° C. and approximately600° C., are shown in FIGS. 5 a and 5 b, respectively. The crystallitesize of approximately 45 nm is calculated using Scherrer's equation(Cullity, B. D., 1978. Elements of S-Ray Diffraction, Addison-Weley,Mass.) for monodispersed, submicron sized, spherical ZrO₂ particlesafter calcination at approximately 400° C. Moreover, decrease in theFWHM is observed in FIG. 5 with increase in the calcination temperature.

TEM analysis reveals that the ZrO₂ nanoparticles of size approximately20 to approximately 25 nm synthesized at large R value 60 form“loose-agglomerates” as schematically shown in FIG. 6 a. The formationof loose-agglomerates is due to high nucleation rates associated withlarge R value. By contrast, XRD and HRTEM analysis and correspondingSAED patterns obtained for monodispersed, submicron sized, sphericalZrO₂ particles, after calcination at approximately 400° C., indicatethat these particles are made up of small nanocrystallites of sizeapproximately 45 nm, as schematically shown in FIG. 6 b. It appears thatZrO₂ nanocrystallites form “hard-aggregates” under the processingconditions of R 5, [HPC]) 1.0 g/L, due to very slow kinetics ofhydrolysis and condensation reactions associated with low R value.

The submicron sized ZrO₂ particles of size approximately 500 toapproximately 600 nm are expected to exhibit monoclinic crystalstructure at room temperature, as the particle size is much greater thanthe critical size of approximately 6 nm to have any thermodynamic effectfor high-temperature metastable tetragonal phase stabilization. Thetendency of the ZrO₂ nanocrystallites to form hard-aggregates andloose-agglomerates is, however, observed to significantly affect itsphase transformation behavior at higher temperatures.

The temperature of metastable tetragonal polymorph of ZrO₂ is stabilizedat room temperature within the monodispersed submicron sized(approximately 500 to approximately 600 nm) spherical ZrO₂ particleswithout doping any trivalent impurity. Various theories have beenproposed for the stabilization of metastable tetragonal phase innanocrystalline ZrO₂ at room temperature.

Garvie, (R. C. J Phy. chem, 1965, 69, 1238) experimentally (using XRD)and using thermodynamic calculations, showed the existence of a criticalsize of 20 nm, below which the metastable tetragonal phase is stable innanocrystalline ZrO₂ and above which the monoclinic phase is stable.Mitsuhashi et al, (J. Am. Ceram. Soc. 1974, 57, 97) however, showed thatthe metastable tetragonal phase can be stabilized in ZrO₂nanocrystallites of size greater than approximately 30 nm due to thestrain energy involved at the interphase boundaries resulting from thesimultaneous presence of monoclinic and tetragonal phases within thecrystallites. By HRTEM analysis Nitsche et al further showed that thecritical size for 100% tetragonal phase stabilization in nanocrystallineZrO₂ is about 6 nm, above which ZrO₂ nanocrystallites exist as acore-shell particles with tetragonal phase, as a core and monoclinicphase as a shell. In our invention, ZrO2 nanocrystallites of size assmall as about 20 to about 25 nm are synthesized (FIG. 1 a) which arelarger than the critical size of about 6 nm for the stabilization of theabout 100% tetragonal phase. This is probably the reason for theappearance of tetragonal as well as monoclinic phases when these ZrO₂nanocrystallites are calcined at the crystallization temperature of 400degrees C. With increased calcinations temperature above 400 degrees C.,the phase transformation possibly proceeds in a manner as describedschematically in FIG. 6 c.

The tetragonal-to-monoclinic phase transformation in ZrO₂ is athermal innature. As a result, a specific amount of monoclinic phase is formed ateach calcination temperature, as observed in FIG. 3. As mentionedearlier, monodispersed, submicron sized (approximately 500 toapproximately 600 nm), spherical ZrO₂ particles are composed of smallnanocrystallites of size approximately 45 nm after calcination at 400°C. The nanocrystallite size of approximately 45 nm is also larger thanthe predicted and observed critical size of approximately 30 nm10 andapproximately 6 nm11,12 respectively for approximately 100% metastabletetragonal phase stabilization. However, interestingly, no monoclinicphase formation is observed after crystallization of submicron sizedZrO₂ particles at 400° C., FIG. 4.

Moreover, the nanocrystallites within the submicron sized ZrO2 particlesare observed to grow due to calcination at 600° C., which is indicatedby the decrease in the FWHM of the (111)t peak with increase in thecalcination temperature. Even after the growth of the nanocrystallitesabove approximately 45 nm size, no tetragonal to monoclinic phasetransformation is observed at approximately 600° C. Hence, thetetragonal-to-monoclinic phase transformation appears to be suppressedwithin the submicron sized ZrO₂ particles at 600° C. Thus, the phaseevolution behavior exhibited by the monodispersed, submicron sized(approximately 500 to approximately 600 nm), spherical ZrO₂ particles isin contrast with that of ZrO₂ nanocrystallites of size approximately 20to approximately 25 nm.

It is noted that ZrO2 nanocrystallites (approximately 45 nm) formhard-aggregates of size approximately 500 to approximately 600 nm, underthe processing conditions of R 5, [HPC]) 1.0 g/L, while ZrO₂nanocrystallites of size approximately 20 to approximately 25 nm,synthesized under the processing conditions of R) 60, [HPC]) 1.0 g/L,form loose-agglomerates. It appears that due to the formation ofhard-aggregates, the tetragonal-to-monoclinic phase transformation,which is accompanied by volume expansion, is suppressed at approximately400° C. and approximately 600° C. As a result, monodispersed, submicronsized (approximately 500 to approximately 600 nm), spherical ZrO₂particles having metastable tetragonal crystal structure aresuccessfully synthesized in the present investigation.

The stabilization of metastable of tetragonal phase via proposedmechanism, which involves the suppression of volume increase associatedwith the tetragonal-to-monoclinic phase transformation, due to denseagglomeration of nanocrystallites within monodispersed, submicron sized(approximately 500 to approximately 600 nm), spherical ZrO₂ particles,is supported by the following observations. First, the volume expansionassociated with the tetragonal to monoclinic phase transformation wouldcause many stresses and strains to be included in the structure thatmight lead to fracture of the particles. However, no such type offracture of monodispersed, submicron sized (approximately 500 toapproximately 600 nm), spherical ZrO₂ particles has been observed, whichsupports the stabilization of tetragonal phase in the large sizedparticles. Second, there is substantial evidence (obtained via HRTEM) oflittle or no free volume in the monodispersed, submicron sized(approximately 500 to approximately 600 nm), spherical ZrO₂ particles.Analogous to the glass transition in polymers, if there were free volumein these large particles, this excess free volume would permit the phasetransition to take place. Finally, considering the precursors involvedduring the sol gel synthesis of ZrO₂ particles, there is no evidence ofany group III impurity that might be otherwise stabilizing thetetragonal phase.

Nanosized (approximately 20 to approximately 25 nm) and submicron sized(approximately 500 to approximately 600 nm), monodispersed, sphericalZrO₂ particles are successfully synthesized using the sol-gel technique.The tendency of ZrO₂ nanocrystallites (approximately 45 nm) to formhard-aggregates is observed to be responsible for the high-temperaturemetastable tetragonal phase stabilization, at room temperature, withinthe submicron sized ZrO₂ particles.

While the invention has been described, disclosed, illustrated and shownin various terms of certain embodiments or modifications which it haspresumed in practice, the scope of the invention is not intended to be,nor should it be deemed to be, limited thereby and such othermodifications or embodiments as may be suggested by the teachings hereinare particularly reserved especially as they fall within the breadth andscope of the claims here appended.

1-24. (canceled)
 25. Monodispersed, spherical particles of approximately10 to approximately 600 nm, which exhibit metastable tetragonal crystalstructure at room temperature, wherein said particles are synthesizedusing a sol-gel technique, are approximately 100% in the tetragonalstate, and are composed of a ceramic oxide, and being composed of asingle, pure oxide, which is free of other foreign oxides.
 26. Themonosdispersed spherical particles, as in claim 25, wherein said ceramicoxide is selected from the group consisting of zirconium oxide, tinoxide, titanium oxide and indium oxide.
 27. The monodispersed particles,as in claim 25 wherein said particles are of the size approximately 10to approximately 30 nm.
 28. The monodispersed particles, as in claim 25,wherein said particles are of the size approximately 500 toapproximately 600 nm.
 29. A nanocrystalline ZrO₂ powder, comprising:monodispersed, spherical ZrO₂ particles of approximately 10 toapproximately 600 nm, synthesized using a sol-gel technique, that arepure and free of foreign oxides and exhibit metastable tetragonalcrystal structure at room temperature.
 30. The nanocrystalline powder inclaim 29 wherein said particles are in the approximately 100% tetragonalphase, and are pure and free of foreign oxides.